Ionic liquid substituted polysaccharide compounds and methods of use thereof

Abstract

The present disclosure relates, in one aspect, to compounds and / or compositions comprising an ionic liquid substituted polysaccharide of formula (I). In another aspect, the present disclosure relates to films comprising the compound and / or composition of formula (I). In another aspect, the present disclosure relates to methods for sequestering and / or separating carbon dioxide (CO2) from a mixture comprising CO2 and at least one additional gas with the compounds and / or compositions of the present disclosure and / or films, powders, or fibers comprising the same.

Description

[0001] TITLE OF THE INVENTION

[0002] Ionic Liquid Substituted Polysaccharide Compounds and Methods of Use Thereof

[0003] CROSS-REFERENCE TO RELATED APPLICATIONS

[0004] This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application No. 63 / 519,440, filed August 14, 2023, which is incorporated herein by reference in its entirety.

[0005] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0006] This invention was made with government support under Award Number 2104375 and Award Number 2104376 awarded by the National Science Foundation. The government has certain rights in the invention.

[0007] BACKGROUND

[0008] Materials derived from bio-based, renewable sources are highly desirable, at least as a consequence of increasing environmental concerns, such as global warming and / or plastic pollution. This concern has led to an explosion in research encompassing sustainable polymers that can exhibit similar and / or improved mechanical, thermal, and / or electronic properties to traditional, petroleum-based polymeric materials.

[0009] Thus, there is a need in the art for biologically sourced, polymeric materials with mechanical, thermal, and / or electronic properties which are similar to, or represent an improvement over, traditional petroleum-based polymeric materials, and methods of use thereof. The present disclosure addresses this need.

[0010] BRIEF SUMMARY

[0011] In one aspect, the disclosure provides a compound of formula (I), or a salt, solvate, stereoisomer, or isotopologue thereof, wherein R1a, R1b, R2a, R2b, R2c, R2d, L1, L2, Y1, and Y2are defined elsewhere herein:

[0012]

[0013] In certain embodiments, the compound of formula (I) is a compound of formula (la):

[0014] In another aspect, the disclosure provides a film comprising the compound of the disclosure. In certain embodiments, the film is at least partially resistant to mechanical deformation.

[0015] In another aspect, the disclosure provides a powder comprising the compound of the disclosure.

[0016] In another aspect, the disclosure provides a fiber comprising the compound of the disclosure.

[0017] In another aspect, the disclosure provides a method of sequestering carbon dioxide (CO2) and / or separating CO2from a mixture comprising CO2and at least one additional gas, the method comprising contacting the compound of the disclosure, the film of the disclosure, the powder of the disclosure, or the fiber of the disclosure with the mixture. In certain embodiments, the additional gas comprises at least one selected from the group consisting of nitrogen (N2) and oxygen (O2). In certain embodiments, the mixture comprises air.

[0018] BRIEF DESCRIPTION OF THE FIGURES

[0019] The drawings illustrate generally, by way of example, but not by way of limitation, various embodiments of the present application.

[0020] FIG. 1 depicts a non-limiting dual-ionic liquid (DIL) functionalized cellulose compound of the present disclosure and a mono-ionic liquid functionalized compound, wherein the ionic liquid groups are indicated. FIG. 2 provides an overlay of FTIR spectra for certain exemplary CELL-C8 dual-IL functionalized cellulosic materials (i.e., CELL-C8-tri-im, CELL-C8-Br, and CELL-C8-NTf2).

[0021] FIG. 3 provides an overlay of representative stress-strain curves for certain exemplary dual-IL functionalized cellulosic materials (i.e., CELL-C4-NTf2, CELL-C8-NTf2, and CELL- C12-NTf2)

[0022] FIG. 4 provides Wide-Angle X-ray Scattering (WAXS) and Small-Angle X-ray Scattering (SAXS) combined X-ray scattering at 20 °C as a function of scattering vector (q) for certain exemplary dual ionic liquid (IL) functionalized cellulosic materials.

[0023] FIGs. 5A-5B provides graphs depicting ionic conductivity as a function of temperature (FIG. 5A) and Tg-normalized conductivity curves (FIG. 5B) for certain exemplary dual-IL cellulosic materials of the CELL-Cx-NTf2series.

[0024] FIGs. 6A-6D provide exemplary photographs (FIGs. 6A-6B) and graphs (FIGs. 6C-6D) demonstrating the shape-memory properties of certain exemplary dual-IL cellulosic materials of the present disclosure (i.e., CELL-C8-NTf2). The shape-fixity ratio quantifies the ability of the polymer to fix a temporary shape and is the deformation after the stress was released with respect to the maximum deformation. The shape-recovery ration quantifies the ability of the polymer to recover its original shape and was calculated as the total deformation recovered with respect to the maximum deformation reached.

[0025] FIG. 7 provides a graph depicting ionic conductivity as a function of temperature for certain exemplary dual-IL cellulosic materials of the disclosure (e.g., CELL-TRI-IM-BU-NTf2and CELL-TRI-IM-ET-NTF2)

[0026] FIG. 8 provides a graph depicting thermal stability of certain exemplary single-IL cellulosic materials of the disclosure.

[0027] DETAILED DESCRIPTION OF THE INVENTION

[0028] Reference will now be made in detail to certain embodiments of the disclosed subject matter, examples of which are illustrated in part in the accompanying drawings. While the disclosed subject matter will be described in conjunction with the enumerated claims, it will be understood that the exemplified subject matter is not intended to limit the claims to the disclosed subject matter. Throughout this document, values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a range of “about 0.1% to about 5%” or “about 0.1% to 5%” should be interpreted to include not just about 0.1% to about 5%, but also the individual values (e.g. , 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%) within the indicated range. The statement “about X to Y” has the same meaning as “about X to about Y,” unless indicated otherwise. Likewise, the statement “about X, Y, or about Z” has the same meaning as “about X, about Y, or about Z,” unless indicated otherwise.

[0029] In this document, the terms “a,” “an,” or “the” are used to include one or more than one unless the context clearly dictates otherwise. The term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. The statement “at least one of A and B” or “at least one of A or B” has the same meaning as “A, B, or A and B.” In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Any use of section headings is intended to aid reading of the document and is not to be interpreted as limiting; information that is relevant to a section heading may occur within or outside of that particular section. All publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference.

[0030] In the methods described herein, the acts can be carried out in any order, except when a temporal or operational sequence is explicitly recited. Furthermore, specified acts can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed act of doing X and a claimed act of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

[0031] Description

[0032] Polymers like cellulose, a naturally occurring polysaccharide that provides rigidity in plants, can offer strong mechanical properties while demonstrating sustainability, and can be utilized in the preparation of a variety of biobased monomers and functionalized biomaterials. Cellulose comprises repeating glucose units and is characterized by its semi-crystalline fiber morphologies and high functionality. Microcrystalline cellulose (MCC), a commonly used commercial derivative of cellulose, is a nanostructured material produced from an acidic hydrolysis process which removes amorphous regions within the cellulose structure. Regardless of the degree of crystallinity, cellulose can be chemically altered to adopt more favorable morphologies due to the biopolymer’s multiple hydroxyl groups on each glucose unit. For example, cellulose can be acetylated, which can alter the extent of chain stiffness, cross-linking, and intermolecular interactions between the polymer chains. Chemically modifying cellulose has led to several new applications in polymer and biomedical research as many of the resulting materials have been used in drug delivery, tissue engineering, optical films, and in energy storage.

[0033] A relatively recent method for modifying cellulose is utilizing the “click” azide-alkyne 1,3-dipolar cycloaddition strategy. The hydroxyl groups on cellulose (e.g., the primary alcohol) can be converted to azides or alkyne-containing groups and then undergo cyclization with a complementary alkyne or azide to yield a substituted 1,2, 3 -triazole ring, typically under copper- catalyzed conditions. For example, 6-deoxy-6-aminopropargylcellulose can undergo ‘click’ cyclization with a variety of azido-functionalized materials as indicated by NMR (nuclear magnetic resonance) and FTIR (Fourier transform infrared) spectroscopy.

[0034] Despite all of the groundbreaking work on functionalizing cellulose using azide-alkyne ‘click’ cyclization, further quatemizing the resulting 1,2,3-triazole ring into an ionic liquid (IL), thereby creating a poly(ionic liquid), has not been fully explored. Poly(ionic liquid)s (PILs) are a sub-class of ion-containing polymers whereby an IL group is covalently attached pendant to the polymer backbone. PILs are unique in that they often retain the tunable thermal, chemical and conductive properties of the ‘free’ ionic liquid, but provide the benefit of mechanical stability. As a result, PILs have been utilized in numerous applications ranging from electroactive devices to gas separation membranes. Through altering the nature of the backbone, and ionic liquid components (cation and anion), a desired set of thermal and conductive properties can be achieved to accomplish a specific application.

[0035] Ion transport in PILs relates to a number of polymer properties, including molecular weight, glass transition temperature ( Tg), morphology, and ion aggregation. Larger counterions that have a greater free volume tend to lower Tgand increase conductivity, due to an increased ability of the counteranion to “ion hop” throughout the polymer matrix. Several research teams have specifically analyzed this trend, measuring ionic conductivities of a variety of counteranions, including tetrafluoroborate [BF4], triflate [OTf], and bis(trifluoromethylsulfonyl)imide [NTf2],

[0036] It was determined that, below the Tg, ionic conductivity is primarily determined by the counterion’s ability to hop throughout the glassy matrix of the polymer. Temperature dependence of ionic conductivity was found to exhibit Arrhenius behavior below the Tgand changed to non-linear behavior at temperatures above the Tg. This change can be attributed to the dependence of segmental dynamics among other factors, which are more pertinent at temperatures above Tg.

[0037] Both theory and experiment suggest that ionic aggregation is more likely if the polymer is less polar; however, aggregation may not be detrimental to ionic conductivity if the aggregates are percolated throughout the matrix rather than existing as discrete, localized clusters.

[0038] The present disclosure relates, in one aspect, to the functionalization of microcrystalline cellulose with two ionic liquid units (i.e., dual-IL functionalized cellulosic materials). Taking advantage of an azide-alkyne click cycloaddition approach, the alkynes chosen for the present study also contain an imidazole ring, thereby allowing for quatemization of both the 1,2,3- triazole and imidazole rings simultaneously, resulting in two IL groups per glucose unit (e.g., the degree of substitution (DS) of certain exemplary compositions being approximately 0.87-0.90).

[0039] In certain embodiments, the length of the alkyl tether between the two IL groups was varied in order to determine the breadth of thermal, mechanical, and conductive properties of the resulting derivatives. Through this dual-IL functionalized route, a significant decrease in the Tgwas observed (below 0 °C) as compared to previously reported “mono-IL” substituted cellulosic materials. Films of the dual-IL materials were found to be much more flexible and thus mechanical properties (stress-strain at break) were acquired in addition to conductivities, the latter of which were found to be on the order of 10-7to 10-6S / cm at 30 °C.

[0040] Thus, the present disclosure describes certain exemplary dual-IL functionalized cellulosic materials and the mechanical, thermal, and / or electronic properties thereof.

[0041] Definitions The term “about” as used herein can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range, and includes the exact stated value or range.

[0042] The term “alkenyl” as used herein refers to straight and branched chain and cyclic alkyl groups as defined herein, except that at least one double bond exists between two carbon atoms. Thus, alkenyl groups have from 2 to 40 carbon atoms, or 2 to about 20 carbon atoms, or 2 to 12 carbon atoms or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to vinyl, -CH=C=CH2, -CH=CH(CH3), -CH=C(CH3)2, -C(CH3)=CH2, - C(CH3)=CH(CH3), -C(CH2CH3)=CH2, cyclohexenyl, cyclopentenyl, cyclohexadienyl, butadienyl, pentadienyl, and hexadienyl among others.

[0043] The term “alkoxy” as used herein refers to an oxygen atom connected to an alkyl group, including a cycloalkyl group, as are defined herein. Examples of linear alkoxy groups include but are not limited to methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, and the like. Examples of branched alkoxy include but are not limited to isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, isohexyloxy, and the like. Examples of cyclic alkoxy include but are not limited to cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, and the like. An alkoxy group can include about 1 to about 12, about 1 to about 20, or about 1 to about 40 carbon atoms bonded to the oxygen atom, and can further include double or triple bonds, and can also include heteroatoms. For example, an allyloxy group or a methoxyethoxy group is also an alkoxy group within the meaning herein, as is a methylenedioxy group in a context where two adjacent atoms of a structure are substituted therewith.

[0044] The term “alkynyl” as used herein refers to straight and branched chain alkyl groups, except that at least one triple bond exists between two carbon atoms. Thus, alkynyl groups have from 2 to 40 carbon atoms, 2 to about 20 carbon atoms, or from 2 to 12 carbons or, in some embodiments, from 2 to 8 carbon atoms. Examples include, but are not limited to -C≡CH, - C ≡C(CH3), -C ≡C(CH2CH3), -CH2C ≡CH, -CH2C ≡C(CH3), and -CH2C≡C(CH2CH3) among others.

[0045] The term “alkyl” as used herein refers to straight chain and branched alkyl groups and cycloalkyl groups having from 1 to 40 carbon atoms, 1 to about 20 carbon atoms, 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms. Examples of straight chain alkyl groups include those with from 1 to 8 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- hexyl, n-heptyl, and n-octyl groups. Examples of branched alkyl groups include, but are not limited to, isopropyl, iso-butyl, sec-butyl, t-butyl, neopentyl, isopentyl, and 2,2-dimethylpropyl groups. As used herein, the term “alkyl” encompasses n-alkyl, isoalkyl, and anteisoalkyl groups as well as other branched chain forms of alkyl. Representative substituted alkyl groups can be substituted one or more times with any of the groups listed herein, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups.

[0046] The term “amine” as used herein refers to primary, secondary, and tertiary amines having, e.g., the formula N(group)? wherein each group can independently be H or non-H, such as alkyl, aryl, and the like. Amines include but are not limited to R-NH2, for example, alkylamines, arylamines, alkylarylamines; R2NH wherein each R is independently selected, such as dialkylamines, diarylamines, aralkylamines, heterocyclylamines and the like; and RiN wherein each R is independently selected, such as trialkylamines, dialkylarylamines, alkyldiarylamines, triarylamines, and the like. The term “amine” also includes ammonium ions as used herein.

[0047] The term “aryl” as used herein refers to cyclic aromatic hydrocarbon groups that do not contain heteroatoms in the ring. Thus aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenylenyl, anthracenyl, and naphthyl groups. In some embodiments, aryl groups contain about 6 to about 14 carbons in the ring portions of the groups. Aryl groups can be unsubstituted or substituted, as defined herein. Representative substituted aryl groups can be mono-substituted or substituted more than once, such as, but not limited to, a phenyl group substituted at any one or more of 2-, 3-, 4-, 5-, or 6-positions of the phenyl ring, or a naphthyl group substituted at any one or more of 2- to 8-positions thereof. Use of the term “aryl” in combination with another term (e.g., iodide, chloride, boronic acid, and magnesium halide, inter alia), indicates that the aryl group is substituted at one or more positions with the substituent defined by the term used in the combination. For example, an aryl chloride indicates that the aryl is substituted with at least one chloride.

[0048] The term “counter anion” as used herein refers to a negatively charged ion that accompanies a cationic species (i.e. positively charged ion) in order to maintain electric neutrality. For example, the chloride ion (Cl-) is the counter anion to sodium (Na+) in NaCl. Non- limiting examples of counter anions include F-, Cl-, Br-, I-, H-, N3-, PhCH=CHCH2-, PhCH- CH=CH2, F3CS(=O)2O- (OTf), (F3CS(=O)2)2N- (NTf2), F3CC(=O)O‘ (TFA), BF4-, and PF6-.

[0049] The term “cycloalkyl” as used herein refers to cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups. In some embodiments, the cycloalkyl group can have 3 to about 8-12 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 4, 5, 6, or 7. Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like. Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined herein. Representative substituted cycloalkyl groups can be mono-substituted or substituted more than once, such as, but not limited to, 2,2-, 2,3-, 2,4- 2,5- or 2, 6-di substituted cyclohexyl groups or mono-, di- or tri- substituted norbomyl or cycloheptyl groups, which can be substituted with, for example, amino, hydroxy, cyano, carboxy, nitro, thio, alkoxy, and halogen groups. The term “cycloalkenyl” alone or in combination denotes a cyclic alkenyl group.

[0050] The terms “halo,” “halogen,” or “halide” group, as used herein, by themselves or as part of another substituent, mean, unless otherwise stated, a fluorine, chlorine, bromine, or iodine atom.

[0051] The term “haloalkyl” group, as used herein, includes mono-halo alkyl groups, poly-halo alkyl groups wherein all halo atoms can be the same or different, and per-halo alkyl groups, wherein all hydrogen atoms are replaced by halogen atoms, such as fluoro. Examples of haloalkyl include trifluoromethyl, 1,1 -dichloroethyl, 1,2-dichloroethyl, 1,3-dibromo-3,3- di fluoropropyl, perfluorobutyl, and the like.

[0052] The term “heteroaryl” as used herein refers to aromatic ring compounds containing 5 or more ring members, of which, one or more is a heteroatom such as, but not limited to, N, O, and S; for instance, heteroaryl rings can have 5 to about 8-12 ring members. A heteroaryl group is a variety of a heterocyclyl group that possesses an aromatic electronic structure. A heteroaryl group designated as a C2-heteroaryl can be a 5-ring with two carbon atoms and three heteroatoms, a 6-ring with two carbon atoms and four heteroatoms and so forth. Likewise a C4- heteroaryl can be a 5-ring with one heteroatom, a 6-ring with two heteroatoms, and so forth. The number of carbon atoms plus the number of heteroatoms sums up to equal the total number of ring atoms. Heteroaryl groups include, but are not limited to, groups such as pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridinyl, thiophenyl, benzothiophenyl, benzofuranyl, indolyl, azaindolyl, indazolyl, benzimidazolyl, azabenzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, imidazopyridinyl, isoxazolopyridinyl, thianaphthalenyl, purinyl, xanthinyl, adeninyl, guaninyl, quinolinyl, isoquinolinyl, tetrahydroquinolinyl, quinoxalinyl, and quinazolinyl groups. Heteroaryl groups can be unsubstituted, or can be substituted with groups as is discussed herein. Representative substituted heteroaryl groups can be substituted one or more times with groups such as those listed herein.

[0053] Additional examples of aryl and heteroaryl groups include but are not limited to phenyl, biphenyl, indenyl, naphthyl (1 -naphthyl, 2-naphthyl), N-hydroxytetrazolyl, N-hydroxytriazolyl, N-hydroxyimidazolyl, anthracenyl (1-anthracenyl, 2-anthracenyl, 3-anthracenyl), thiophenyl (2-thienyl, 3-thienyl), furyl (2-furyl, 3-furyl) , indolyl, oxadiazolyl, isoxazolyl, quinazolinyl, fluorenyl, xanthenyl, isoindanyl, benzhydryl, acridinyl, thiazolyl, pyrrolyl (2-pyrrolyl), pyrazolyl (3 -pyrazolyl), imidazolyl (1 -imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl), triazolyl (1,2,3-triazol-l-yl, l,2,3-triazol-2-yl 1,2, 3 -triazol -4-yl, l,2,4-triazol-3-yl), oxazolyl (2-oxazolyl,

[0054] 4-oxazolyl, 5-oxazolyl), thiazolyl (2-thiazolyl, 4-thiazolyl, 5-thiazolyl), pyridyl (2-pyridyl, 3-pyridyl, 4-pyridyl), pyrimidinyl (2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl), pyrazinyl, pyridazinyl (3- pyridazinyl, 4-pyridazinyl, 5-pyridazinyl), quinolyl (2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl), isoquinolyl (1-isoquinolyl,

[0055] 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl), benzo[b]furanyl (2-benzo[b]furanyl, 3-benzo[b]furanyl, 4-benzo[b]furanyl, 5-benzo[b]furanyl, 6-benzo[b]furanyl, 7-benzo[b]furanyl), 2,3-dihydro-benzo[b]furanyl (2-(2,3-dihydro- benzo[b]furanyl), 3-(2,3-dihydro-benzo[b]furanyl), 4-(2,3-dihydro-benzo[b]furanyl),

[0056] 5-(2,3-dihydro-benzo[b]furanyl), 6-(2,3-dihydro-benzo[b]furanyl), 7-(2,3-dihydro- benzo[b]furanyl), benzo[b]thiophenyl (2-benzo[b]thiophenyl, 3-benzo[b]thiophenyl,

[0057] 4-benzo[b]thiophenyl, 5-benzo[b]thiophenyl, 6-benzo[b]thiophenyl, 7-benzo[b]thiophenyl), 2,3-dihydro-benzo[b]thiophenyl, (2-(2,3-dihydro-benzo[b]thiophenyl), 3-(2,3-dihydro- benzo[b]thiophenyl), 4-(2,3-dihydro-benzo[b]thiophenyl), 5-(2,3-dihydro-benzo[b]thiophenyl),

[0058] 6-(2,3-dihydro-benzo[b]thiophenyl), 7-(2,3-dihydro-benzo[b]thiophenyl), indolyl (1-indolyl,

[0059] 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl), indazole (1-indazolyl,

[0060] 3-indazolyl, 4-indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl), benzimidazolyl (1 -benzimidazolyl, 2-benzimidazolyl, 4-benzimidazolyl, 5-benzimidazolyl, 6-benzimidazolyl, 7-benzimidazolyl, 8-benzimidazolyl), benzoxazolyl (1-benzoxazolyl, 2-benzoxazolyl), benzothiazolyl (1-benzothiazolyl, 2-benzothiazolyl, 4-benzothiazolyl, 5 -benzothiazolyl, 6-benzothiazolyl, 7-benzothiazolyl), carbazolyl (1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl), 5H-dibenz[b,f]azepine (5H-dibenz[b,f]azepin-l-yl, 5H-dibenz[b,f]azepine-2-yl, 5H-dibenz[b,f]azepine-3-yl, 5H-dibenz[b,f]azepine-4-yl, 5H-dibenz[b,f]azepine-5-yl), 10,11-dihydro-5H-dibenz[b,f]azepine (10,11-dihydro-5H-dibenz[b,f]azepine-l-yl, 10,11-dihy dro-5H-dibenz[b,f]azepine-2-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-3-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-4-yl, 10,11-dihydro-5H-dibenz[b,f]azepine-5-yl), and the like.

[0061] The term “independently selected from” as used herein refers to referenced groups being the same, different, or a mixture thereof, unless the context clearly indicates otherwise. Thus, under this definition, the phrase “X1, X2, and X3are independently selected from noble gases” would include the scenario where, for example, X1, X2, and X3are all the same, where X1, X2, and X3are all different, where X1and X2are the same but X3is different, and other analogous permutations.

[0062] The term “linker” as used herein refers to a chemically inert region between two linked molecules (e.g., a catalyst complex and a substrate).

[0063] The term “substituted” as used herein in conjunction with a molecule or an organic group as defined herein refers to the state in which one or more hydrogen atoms contained therein are replaced by one or more non-hydrogen atoms. The term “functional group” or “substituent” as used herein refers to a group that can be or is substituted onto a molecule or onto an organic group. Examples of substituents or functional groups include, but are not limited to, a halogen (e.g., F, Cl, Br, and I); an oxygen atom in groups such as hydroxy groups, alkoxy groups, aryloxy groups, aralkyloxy groups, oxo(carbonyl) groups, carboxyl groups including carboxylic acids, carboxylates, and carboxylate esters; a sulfur atom in groups such as thiol groups, alkyl and aryl sulfide groups, sulfoxide groups, sulfone groups, sulfonyl groups, and sulfonamide groups; a nitrogen atom in groups such as amines, hydroxyamines, nitriles, nitro groups, N- oxides, hydrazides, azides, and enamines; and other heteroatoms in various other groups. Non- limiting examples of substituents that can be bonded to a substituted carbon (or other) atom include F, Cl, Br, I, OR, OC(O)N(R)2, CN, NO, NO2, ONO2, azido, CF3, OCF3, R, O (oxo), S (thiono), C(O), S(O), methylenedioxy, ethylenedi oxy, N(R)2, SR, SOR, SO2R, SO2N(R)2, SO3R, C(O)R, C(O)C(O)R, C(O)CH2C(O)R, C(S)R, C(O)OR, OC(O)R, C(O)N(R)2, OC(O)N(R)2, C(S)N(R)2, (CH2)O-2N(R)C(0)R, (CH2)O-2N(R)N(R)2, N(R)N(R)C(O)R, N(R)N(R)C(O)OR, N(R)N(R)CON(R)2, N(R)SO2R, N(R)SO2N(R)2, N(R)C(O)OR, N(R)C(O)R, N(R)C(S)R, N(R)C(O)N(R)2, N(R)C(S)N(R)2, N(COR)COR, N(0R)R, C(=NH)N(R)2, C(O)N(OR)R, and C(=NOR)R, wherein R can be hydrogen or a carbon-based moiety; for example, R can be hydrogen, (C1-C100) hydrocarbyl, alkyl, acyl, cycloalkyl, aryl, aralkyl, heterocyclyl, heteroaryl, or heteroarylalkyl; or wherein two R groups bonded to a nitrogen atom or to adjacent nitrogen atoms can together with the nitrogen atom or atoms form a heterocyclyl.

[0064] Compositions

[0065] In one aspect, the present disclosure provides a compound of formula (I), or a salt, solvate, stereoisomer, or isotopologue thereof: wherein: each occurrence of R1aand R1bis independently selected from the group consisting of

[0066] OH, NH2, N3, , and , wherein less than about 50% of the R1aand R1bsubstituents are OH, NH2, or N3; each occurrence of L1, L2, and L3is independently selected from the group consisting of optionally substituted C1-C12alkylenyl and optionally substituted C1-C12heteroalkylenyl; each occurrence of Y1and Y2is independently selected from the group consisting of O and NR2e;

[0067] R2a, R2b, R2C, R2d, and R2eare each independently selected from the group consisting of H, optionally substituted C1-C6alkyl, and C(=O)(optionally substituted C1-C6alkyl); each occurrence of A1is independently selected from the group consisting of

[0068] each occurrence of R3aand R3bis independently selected from the group consisting of optionally substituted C1-C12alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of R4a, R4b, and R4cis independently selected from the group consisting of H, halogen, CN, NO2, ORA, N(RA)(RB), SRA, C(=O)ORA, C(=O)RA, C(=O)N(RA)(RB), S(=O)2RA, S(=O)2ORA, S(=O)2N(RA)(RB), S(=O)RA, S(=O)N(RA)(RB), P(=O)(ORA)(ORB), optionally substituted C1-C6alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of X1is independently a counter anion;

[0069] A2is selected from the group consisting of each occurrence of R5a, R5b, and R5cis independently selected from the group consisting of optionally substituted C1-C12alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of R6a, R6band R6cis independently selected from the group consisting of H, halogen, CN, NO2, ORC, N(RC)(RD), SRC, C(=O)ORc, C(=O)Rc, C(=O)N(Rc)(RD), S(=O)2RC, S(=O)2ORC, S(=O)2N(RC)(RD), S(=O)RC, S(=O)N(RC)(RD), P(=O)(ORC)(ORD), optionally substituted C1-C6alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of T is independently selected from the group consisting of optionally substituted C1-C12alkyl and optionally substituted C1-C12alkoxy each occurrence of X2is independently a counter anion; each occurrence of RA, RB, Rc, and RDis independently selected from the group consisting of H, optionally substituted C1-C6alkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; m is an integer ranging from 100 to 10,000; each occurrence of n is independently an integer ranging from 1 to 200.

[0070] In certain embodiments, less than about 50, 49, 48, 47, 46, 45, 44, 43, 42, 41, 40, 39, 38,

[0071] 37, 36, 35, 34, 33, 32, 31, 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, or about 1% of the R1aand R1bsubstituents are OH, NH2, or N3.

[0072] In certain embodiments, m is (an integer) selected from the group consisting of about 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200,

[0073] 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700,

[0074] 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200,

[0075] 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, 8000, 8100, 8200, 8300, 8400, 8500, 8600, 8700, 8800, 8900, 9000, 9100, 9200, 9300, 9400, 9500, 9600, 9700, 9800, 9900, and about 10000.

[0076] In certain embodiments, each occurrence of n is an integer selected from the group consisting of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 50, 75, 100, 125, 150, 175, or about 200.

[0077] In certain embodiments, the compound of formula (I) is a compound of formula (la):

[0078] In certain embodiments, L1is -CH2-. In certain embodiments, L1is -CH2OCH2CH2-.

[0079] In certain embodiments, L2is -CH2-. In certain embodiments, L2is -CH2OCH2CH2-.

[0080] In certain embodiments, each occurrence of L1and L2is -CH2-. In certain embodiments, each occurrence of L1and L2is -CH2OCH2CH2-. In certain embodiments, each occurrence of L1and L2is -CH2- and each occurrence of Y1and Y2is O. In certain embodiments, each occurrence of L1and L2is -CH2- and each occurrence of Y1and Y2is NH. In certain embodiments, each occurrence of L1and L2is -CH2OCH2CH2- and each occurrence of Y1and Y2is O.

[0081] In certain embodiments, R2ais H. In certain embodiments, R2bis H. In certain embodiments, R2cis H. In certain embodiments, R2dis H. In certain embodiments, R2eis H.

[0082] In certain embodiments, Y1is -O-. In certain embodiments, Y1is -NH-.

[0083] In certain embodiments, Y2is -O-. In certain embodiments, Y2is -NH-.

[0084] In certain embodiments, R3ais C1-C6alkyl. In certain embodiments, R3ais ethyl. In certain embodiments, R3ais butyl.

[0085] In certain embodiments, R3bis C1-C6alkyl. In certain embodiments, R3bis ethyl. In certain embodiments, R3bis butyl.

[0086] In certain embodiments, R4ais H. In certain embodiments, R4ais -(CH2)1-5CH3. In certain embodiments, R4ais -CH(CH3)2. In certain embodiments, R4ais -CH2CH(CH3)2. In certain embodiments, R4ais -(CH2CH2O)1-6(CH2)0-5CH3. In certain embodiments, R4ais . In certain embodiments, R4ais In certain embodiments, R4ais

[0087] In certain embodiments, R4bis H. In certain embodiments, R4bis -(CH2)1-5CH3. In certain embodiments, R4bis -CH(CH3)2. In certain embodiments, R4bis -CH2CH(CH3)2. In certain embodiments, R4bis -(CH2CH2O)1-6(CH2)0-5CH3. In certain embodiments, R4bis . In certain embodiments, R4bis In certain embodiments, R4bis

[0088] In certain embodiments, R4cis H. In certain embodiments, R4cis -(CH2)1-5CH3. In certain embodiments, R4cis -CH(CH3)2. In certain embodiments, R4cis -CH2CH(CH3)2. In certain embodiments, R4cis -(CH2CH2O)1-6(CH2)0-5CH3. In certain embodiments, R4cis In certain embodiments, R4cis In certain embodiments, R4cis

[0089] In certain embodiments, X1is N(S(=O)2CF3)2(NTf2). In certain embodiments, X1is OS(=O)2CF3(OTf). In certain embodiments, X1is OC(=O)CH3(OAc). In certain embodiments, X1is OC(=O)CF3. In certain embodiments, X1is N(CN)2, In certain embodiments, X1is PF6. BF4. In certain embodiments, X1is Br. In certain embodiments, X1is OH. In certain embodiments, X1is HCO3. In certain embodiments, two occurrences of X1comprise COs2'.

[0090] In certain embodiments, A1is In certain embodiments, A1is

[0091] In certain embodiments, R5ais C1-C6alkyl. In certain embodiments, R5ais ethyl. In certain embodiments, R5bis C1-C6alkyl. In certain embodiments, R5bis ethyl. In certain embodiments, R5cis C1-C6alkyl. In certain embodiments, R5cis ethyl.

[0092] In certain embodiments, R6ais H. In certain embodiments, R6ais -(CH2)1-5CH3. In certain embodiments, R6ais -CH(CH3)2. In certain embodiments, R6ais -CH2CH(CH3)2. In certain embodiments, R6ais -(CH2CH20)1-6(CH2)0-5CH3. In certain embodiments, R6ais In certain embodiments, R6ais . In certain embodiments, R6ais

[0093] In certain embodiments, R6bis H. In certain embodiments, R6bis -(CH2)1-5CH3. In certain embodiments, R6bis -CH(CH3)2. In certain embodiments, R6bis -CH2CH(CH3)2. In certain embodiments, R6bis -(CH2CH2O)1-6(CH2)0-5CH3. In certain embodiments, R6bis . In certain embodiments, R6bis . In certain embodiments, R6bis

[0094] In certain embodiments, R6cis H. In certain embodiments, R6cis -(CH2)i-sCH3. In certain embodiments, R6cis -CH(CH3)2. In certain embodiments, R6cis -CH2CH(CH3)2. In certain embodiments, R6cis -(CH2CH2O)1-6(CH2)0-5CH3. In certain embodiments, R6cis . In certain embodiments, R6cis . In certain embodiments, R6cis X / ^ .

[0095] In certain embodiments, X2is N(S(=O)2CF3)2(NTf2). In certain embodiments, X2is OS(=O)2CF3(OTf). In certain embodiments, X2is OC(=O)CH3(OAc). In certain embodiments, X2is OC(=O)CF3. In certain embodiments, X2is N(CN)2, In certain embodiments, X2is PF6. BF4. In certain embodiments, X2is Br. In certain embodiments, X2is OH. In certain embodiments, X2is HCO3. In certain embodiments, two occurrences of X2comprise CO32-.

[0096] In certain embodiments, A2is . In certain embodiments, A2is

[0097] In certain embodiments, L3is -CH2O(CH2)2-. In certain embodiments, L3is - CH2O(CH2)4-. In certain embodiments, L3is -CH2O(CH2)8-. In certain embodiments, L3is - (CH2)4-. In certain embodiments, L3is -CH2-.

[0098] In certain embodiments, n is 1.

[0099] In certain embodiments, R1ais . In certain embodiments, R1ais . In certain embodiments, R1ais . In certain embodiments, R1ais . In certain embodiments, R1ais

[0100] In certain embodiments, R1bis . In certain embodiments, 1lbis . In certain embodiments, R1bis In certain embodiments, R1bis . In certain embodiments, R1bis

[0101] In certain embodiments, T is In certain embodiments, T is certain embodiments, T is . In certain embodiments, T is . In certain embodiments, T is . In certain embodiments, T is

[0102] In certain embodiments, R1ais . In certain embodiments, R1ais embodiments, R1ais In certain embodiments, R1ais In certain embodiments, R1ais certain embodiments, R1ais

[0103] In certain embodiments, R1bis . In certain embodiments, R1bis In certain embodiments, R1bis . In certain embodiments, R1bis In certain embodiments, R1bis certain embodiments, R1bis

[0104] In another aspect, the present disclosure provides a fdm comprising the compound of formula (I).

[0105] In certain embodiments, the film is resistant to mechanical deformation. In certain embodiments, the film recovers to an original shape after mechanical deformation.

[0106] In another aspect, the present disclosure provides a powder comprising the compound of formula (I).

[0107] In another aspect, the present disclosure provides a film comprising the compound of formula (I).

[0108] Methods

[0109] In another aspect, the present disclosure provide a method of sequestering carbon dioxide (CO2) from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a compound of formula (I).

[0110] In another aspect, the present disclosure provide a method of sequestering carbon dioxide (CO2) from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a film comprising the compound of formula (I).

[0111] In another aspect, the present disclosure provide a method of sequestering carbon dioxide (CO2) from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a powder comprising the compound of formula (I).

[0112] In another aspect, the present disclosure provide a method of sequestering carbon dioxide (CO2) from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a fiber comprising the compound of formula (I).

[0113] In another aspect, the present disclosure provides a method for separating CO2from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a compound of formula (I).

[0114] In another aspect, the present disclosure provides a method for separating CO2from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a film comprising compound of formula (I).

[0115] In another aspect, the present disclosure provides a method for separating CO2from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a powder comprising compound of formula (I).

[0116] In another aspect, the present disclosure provides a method for separating CO2from a mixture comprising CO2and at least one additional gas, the method comprising contacting the mixture with a fiber comprising compound of formula (I).

[0117] In certain embodiments, the additional gas comprises nitrogen (N2). In certain embodiments, the gas comprises oxygen (O2).

[0118] In certain embodiments, the mixture comprises air.

[0119] EXAMPLES

[0120] Various embodiments of the present application can be better understood by reference to the following Examples which are offered by way of illustration. The scope of the present application is not limited to the Examples given herein.

[0121] Materials and Methods

[0122] General

[0123] All chemicals were purchased from Sigma-Aldrich or Fisher Scientific and used without further purification unless stated below. Ultrapure water, having a resistivity of 18 MQ-cm was produced using an ELGA Purelab Ultra filtration device.1H and13C NMR spectra were acquired on a JEOL-ECS 400 MHz spectrometer and the chemical shift values reported are referenced to residual solvent signals in either CDCh (1H, 7.26 ppm;13C, 77.36 ppm) or dimethyl sulfoxide (DMSO)-d6(1H, 2.49 ppm;13C, 39.52 ppm). Cellulose based samples (30 mg) were analyzed using DMSO-d6(0.75 mL) at 100 °C (1H: 12,000 scans;13C: 50,000 scans). FT-IR spectra were taken on a PerkinElmer Spectrum Two spectrometer in transmission mode and the PerkinElmer Spectrum 10 software was used to locate and follow the desired peaks at 1 cm-1resolution over 128 scans. A PerkinElmer 2400 CHNS / O Series II elemental analyzer was used to determine elemental composition (CHNS).

[0124] Thermal Analysis

[0125] Differential scanning calorimetry (DSC) was utilized to determine any thermal transitions of the polymers at a heating rate of 2°C / min on 3-8 mg samples. Glass transition temperatures (Tg) were determined by the inflection point of the curve observed from the second heating cycle. All DSC Tsexperiments were performed in duplicate with an error of ± 2.0 °C. a TA instruments Q550 TGA (thermogravimetric analyzer) was used to evaluate Tds% values (the temperature at which 5% of the material had decomposed) by heating the material under a constant nitrogen flow at a heating rate of 10°C / min.

[0126] Mechanical Property Analysis

[0127] A TA Instruments Q800 DMA in film tension mode with a single frequency of 1 Hz at a heating rate of 5 °C / min was utilized to determine the mechanical properties. DMA experiments were completed in triplicate on each sample. Tensile testing was conducted by cutting rectangular strips of each polymer samples and securing each one with the DMA film clamps. The extension, with a preload force of 0.01 N, was increased at a rate of 20 mm / min at 25 °C until each sample broke or the measurements exceeded the capabilities of the instrument.

[0128] X-ray Scattering Data

[0129] Morphological studies were conducted using a Xeuss 2.0 Dual Source Environmental X- ray Scattering system. Data acquisition was performed under vacuum. A copper x-ray source was used for incident radiation, and a IM pixel Pilatus detector (2D), and a smaller detector for simultaneous SAXS and WAXS acquisition; λ = 1.54189 Å. Acquisition of data was performed for samples using full flux collimation with a 1.2 mm x 1.2 mm slit for a 600 seconds scan-time. Using Datasqueeze 3.0, isotropic 2-D scattering patterns were converted by azimuthal integration to yield a 1-D profile of intensity (a.u.) versus scattering vector q (nm'1). Bragg’s equation was used to calculate values for d -spacing

[0130] Conductivity

[0131] Anhydrous ionic conductivities were measured using a TA Instruments DHR-2 discovery hybrid rheometer equipped with a dielectric accessory and a Keysight Technologies E4980AL / 120 LCR meter was utilized. Each sample was first dried in a vacuum oven for 48 h (60 °C, < 0.1 mm Hg) for 48 hours. Then, the sample (approx, thickness of 500 mm) was placed between two 25 mm stainless steel parallel plate electrodes and the environmental chamber was closed and kept under an atmosphere of dry nitrogen. Temperature was controlled using the environmental chamber in combination with liquid nitrogen. Dielectric permittivity and conductivity were measured isothermally over a frequency range of 20.0 x 106Hz in 10 °C steps with an ac amplitude of ±0.01 V. Samples were kept at a constant axial force (5.0 ± 0.2 N) and soaked at each temperature for 45 min prior to obtaining measurements. The DC conductivity (SDC) was determined from the plateau value observed in the spectral dependence of the conductivity function (s’ = w”e0, where w is the frequency, e” is the dielectric loss, and e0is the vacuum permittivity).

[0132] Film preparation

[0133] Films comprising the functionalized carbohydrate compositions of the present disclosure can be prepared according to any of a number of methods known to those of ordinary skill in the art. The present disclosure provides one exemplary method for preparing such films.

[0134] In certain embodiments, films were prepared by slow evaporation of the polymer composition in DMF (10-15% w / w), optionally wherein heat and / or agitation (e.g., vortexing) was applied to facilitate dissolution of the polymer composition. Once sufficient dissolution occurred so as to provide a homogenous solution, the solution was poured into a Teflon mold assembly (e.g., glass slide, Teflon paper, Teflon mold, and binder clips) and allowed to dry over a period of about 24-48 hours under vacuum. Next, the mold apparatus was disassembled, and the film left intact on the Teflon paper. The sample was next removed from the Teflon paper (e.g., facilitated by tweezers and / or razor) to provide the desired film. Example 1: Exemplary methods for the synthesis of certain dual ionic liquid-functionalized carbohydrate compositions

[0135] The present disclosure provides non-limiting synthetic methods for the preparation of exemplary compositions of the present disclosure.

[0136] In one aspect, in order to covalently bond the dual-IL system to the backbone of cellulose, azide-alkyne ‘click’ cycloaddition chemistry was employed whereby a series of three different alkynyl-substituted imidazoles were reacted with azide-functionalized cellulose (CELL-N3), the latter of which was produced from MCC following methods known to those of ordinary skill in the art (Appl. Polym. Mater. 2021, 3:1097-1106; Scheme 1). The degree of substitution (DS) of CELL-N3was 0.95 as determined from elemental analysis (nitrogen content).

[0137] Scheme 1.

[0138] Alkynyl-substituted imidazoles were prepared as follows. Beginning with the appropriate glycol (Scheme 2; o = 2, 4, and 6) mono-protection with dihydropyran (DHP) under acidic conditions was conducted, resulting in compound 1 (1a-c). A Williamson ether synthesis was then conducted with sodium hydride followed by reaction with propargyl bromide to provide compound 2 (2a-c). Deprotection of the THP group occurred using PPTS (pyridinium p- toluenesulfonate) in refluxing methanol, to provide compound 3 (3a-c), followed by conversion to tosylate 4 (4a-c) using tosyl chloride under basic conditions. Finally, substitution with sodium imidazole provided imidazole 5 (5a-c). All of the propargyl-functionalized imidazoles were isolated as clear, colorless oils and were characterized by1H and13C NMR spectroscopy as well as elemental analysis.

[0139]

[0140] Scheme 2.

[0141] In certain embodiments, alkynyl-substituted imidazoles were prepared as follows.

[0142] Beginning with the appropriate propargyl- or homopropargyl chloride (e.g, Scheme 3; p = 4) halogen-iodine exchange was performed with Nal in acetone, to provide compound 1' (l'a-c). Finally, substitution with sodium imidazole provided imidazole 2' (2'a-c).

[0143] Scheme 3.

[0144] Once the structure and purity of the alkynyl-substituted imidazoles 5a-c and / or 2'a-c were confirmed by NMR spectroscopy and elemental analysis, copper-catalyzed, azide-alkyne ‘click’ cyclization of CELL-N3was undertaken with each of the propargyl-substituted imidazoles, resulting in a series of cellulosic materials. In certain embodiments, cellulosic materials comprising an ethereal linkage are termed CELL-Cx-tri-im, wherein ‘x’ refers the number of carbons of the alkyl chain between the imidazole and the ether oxygen (i.e., x = 2o). Quaternization of both the 1,2,3-triazole and imidazole rings was then accomplished simultaneously by reacting CELL-Cx-tri-im with an excess of alkyl bromide (e.g, ethyl bromide or butyl bromide) in DMF in a high-pressure vessel, resulting in bromide salts CELL- Cx-Br. Anion exchange was completed with lithium bi s(trifluorom ethyl sulfonyl)imide under aqueous conditions, providing the targeted CELL-Cx-NTf2as a series of light tan solids. The DS of the CELL-Cx-NTf2 materials ranged from 0.87 to 0.90 as determined by elemental analysis (sulfur content). Detailed experimental procedures are provided herein for certain exemplary single ionic- and / or dual ionic liquid-functionalized carbohydrate compositions of the present disclosure, prepared according to Schemes 1-5.

[0145] Synthesis of mono-THP-protected 1,8-octane diol (1b)

[0146] To a 500-mL round-bottomed flask equipped with a magnetic stir bar was dissolved 1,8- octanediol (10.00 g, 0.0685 mol) in dichloromethane (200 mL) with mild heating (30-35 °C). Dihydropyran (5.76 g, 0.0685 mol) was then added, followed by a catalytic (10 mg) amount of p- toluenesulfonic acid. The resulting solution stirred for 24-hr at room temperature, then tri ethylamine was added, followed by additional stirring for 1-hr. The contents were then transferred to a separatory funnel and washed with DI water (2 x 100 mL), and brine (100 mL). The organic phase was dried over Na2SO4 / MgSO4, filtered, and the solvent removed under reduced pressure, affording a yellow oil. The crude oil was purified by column chromatography on silica gel using a gradient elution of 0-30% ethyl acetate in hexanes. Purification resulted in 11.35 g (72 %) of a clear, colorless liquid.1H NMR (CDCh): δ 4.54 (t, 1 H, J= 4.4 Hz), 3.82 (m, 1 H), 3.69 (m, 1 H), 3.60 (t, 2 H, J= 6.4 Hz, -CH2-OH), 3.48 (m, 1 H), 3.35 (m, 1 H), 1.79 (m, 1 H), 1.68 (m, 1 H), 1.53 (m, 8 H), 1.33 (m, 8 H).13C NMR (CDCh): 8 98.84, 67.67, 62.82, 62.33,

[0147] 32.78, 30.77, 29.72, 29.44, 29.39, 26.17, 25.72, 25.50, 19.66. Anal. Calcd. For C13H26O3: C

[0148] 67.79, H 11.38. Found: C 67.64, H 11.06.

[0149] Synthesis of mono-THP-protected 1,8-octane diol propargyl ether (2b)

[0150] In a 100-mL round-bottomed flask equipped with a magnetic stir bar under dry argon was charged sodium hydride (2.09 g of a 50-wt% dispersion in oil, 0.0521 mol NaH), and anhydrous THF (15 mL). To this stirred suspension was added dropwise a solution of 1b (10.00 g, 0.0435 mol) in anhydrous THF (50 mL) via an addition funnel. After the addition was completed, the mixture was stirred at room temperature for 1-hr, then propargyl bromide (8.40 g of a 80-wt% solution in toluene, 0.0565 mol propargyl bromide) was added dropwise via an addition funnel. The resulting mixture was stirred at room temperature for 16-hr, then quenched with saturated NH4CI solution (5 mL), followed by dilution with DI water (20 mL). The contents were transferred to a separatory funnel whereupon ethyl acetate (20 mL) was added. After mixing, the organic phase was isolated, washed with DI water (20 mL) and brine, (20 mL), dried over Na2SO4 / MgSO4, filtered, and the solvent removed under reduced pressure, affording a yellow oil. Purification by column chromatography on silica gel using a gradient elution of 0-20% ethyl acetate in hexanes resulted in 8.55 g (73 %) of a clear, colorless liquid.1H NMR (CDl3): 5 4.57 (t, 1 H, 4.0 Hz), 4.13 (d, 2 H, J= 2.4 Hz, -O-CH2-CCH), 3.85 (m, 1 H), 3.73 (m, 1 H), 3.50 (m, 3 H), 3.38 (m, 1 H), 2.43 (t, 1 H, J= 2.4 Hz, term, alkyne), 1.83 (m, 1 H), 1.71 (m, 1 H), 1.59 (m, 8 H), 1.36 (m, 8 H).13C NMR (CDCh): 5 98.83, 80.05, 74.08, 67.64, 62.31, 58.00, 30.79, 29.74, 29.49, 29.40, 29.37, 26.18, 26.05, 25.52, 19.70. Anal. Calcd. For C16H28O3: C 71.60, H 10.52. Found: C 70.51, H 10.29.

[0151] Synthesis of 1,8-octane diol mono-propargyl ether (3b)

[0152] To a 250-mL round-bottomed flask equipped with a magnetic stir bar was dissolved 2b (5.78 g, 0.0216 mol) in methanol (100 mL). Pyridinium tosylate (PPTS, 0.81 g, 3.23 mmol) was then added, followed heating to reflux and stirring overnight. The reaction was then cooled to room temperature and the solvent was removed under reduced pressure, affording a dark yellow oil. The crude oil was purified by column chromatography on silica gel using a gradient elution of 0-30% ethyl acetate in hexanes, resulting in 3.78 g (95 %) of a clear, colorless liquid. 'H NMR (CDCh): 5 4.10 (d, 2 H, J= 2.4 Hz, -O-CH2-CCH). 3.61 (t, 2 H, J= 6.6 Hz), 3.48 (t, 2 H, J= 6.6 Hz), 2.43 (t, 1 H, J= 2.4 Hz, term, alkyne), 1.55 (m, 4 H), 1.31 (m, 8 H).13C NMR (CDCh): δ 79.95, 74.03, 70.17, 62.88, 57.93, 32.66, 29.38, 29.28, 29.25, 25.93, 25.59. Anal. Calcd. For C11H20O2: C 71.70, H 10.94. Found: C 70.61, H 10.74.

[0153] Synthesis of tosylated 1,8-octane diol propargyl ether (4b)

[0154] In a 250-mL round-bottomed flask equipped with a magnetic stir bar was dissolved 3b (3.78 g, 0.0205 mol) in di chloromethane (45 mL). To this stirred solution was added triethylamine (6.02 g, 0.0595 mol) and catalytic DM AP (10 mg). Tosyl chloride (9.78 g, 0.0513 mol) was then added in portions over a 15-min period, followed by stirring of the resulting mixture at room temperature for 16-hr. The reaction was then diluted with additional di chloromethane (200 mL) and transferred to a separatory funnel whereupon the organic phase was washed with 0.1 M HC1 (100 mL) and brine (100 mL), followed by drying over Na2SO4 / MgSO4, filtration, and the solvent removal under reduced pressure. The crude dark-red oil was purified by column chromatography on silica gel using a gradient elution of 5-20% ethyl acetate in hexanes, resulting in 5.15 g (74 %) of a light yellow oil.1H NMR (CDCh): 5 7.68 (d, 2 H, J= 8.4 Hz), 7.25 (d, 2 H, J= 8.4 Hz), 4.02 (d, 2 H, J= 2.4 Hz, -O-C / / 2-CCH), 3.91 (t, 2 H, J = 6.4 Hz), 3.39 (t, 2 H, J= 6.6 Hz), 2.33 (s, 3 H), 2.32 (t, 1 H, J= 2.4 Hz, term, alkyne), 1.53 (m, 2 H), 1.46 (m, 2 H), 1.17 (m, 8 H).13C NMR (CDCh): 6 144.56, 133.00, 129.71, 127.74, 79.90, 74.02, 70.55, 70.02, 57.88, 29.30, 29.00, 28.68, 28.63, 25.80, 25.11, 21.52. Anal. Calcd. For C18H26O4S: C 63.88, H 7.74, S 9.47. Found: C 64.37, H 7.44, S 9.31.

[0155] Synthesis ofimidazoyl 1,8-octane diol propargyl ether (5b)

[0156] In a 250-mL round-bottomed flask equipped with a magnetic stir bar was suspended sodium imidazole (1.28 g, 0.0142 mol) in anhydrous THF (20 mL). A solution of 4b (4.90 g, 0.0145 mol) in anhydrous THF (40 mL) was then added by pipette, and the resulting mixture was stirred for 1-hr at room temperature, followed by 16-hr at reflux. The reaction was then cooled to room temperature, filtered, and the solvent was removed from the filtrate under reduced pressure, affording a yellow oil. Column chromatography on silica gel using a gradient elution of 10-50% acetone in hexanes resulted in 2.73 g (82 %) of a clear, colorless oil. 1HNMR (CDCl3): δ 7.55 (s, 1 H), 7.04 (s, 1 H), 6.88 (s, 1 H), 4.09 (d, 2 H, J= 2.8 Hz, -O-CH2-CCH), 3.91 (t, 2 H, J= 7.0 Hz), 3.46 (t, 2 H, J= 6.6 Hz), 2.38 (t, 1 H, J= 2.8 Hz, term, alkyne), 1.74 (m, 2 H), 1.55 (m, 2 H), 1.32 (m, 8 H).13C NMR (CDCh): δ 136.88, 128.98, 118.67, 79.85, 73.99, 69.99, 57.87, 46.91, 30.88, 29.27, 29.02, 28.82, 26.30, 25.81. Anal. Calcd. For C14H22N2O: C 71.76, H 9.46, N 11.95. Found: C 69.94, H 9.71, N 11.55.

[0157] Synthesis of CELL-C8-tri-im (6b)

[0158]

[0159] In a 250-mL round-bottomed flask with magnetic stirring was dissolved CELL-N3(1.00 g, 5.34 mmol) in DMSO (120 mL) at 100 °C. Once dissolved, the temperature was reduced to 70 °C and 5b (4.20 g, 17.9 mmol) was added, followed by solutions of copper(II) sulfate (43 mg in 10 mL DI water) and sodium ascorbide (110 mg in 10 mL DI water). The resulting mixture was stirred at 70 °C for 48-hr, then cooled and precipitated onto acetone (1.5 L). The solid was isolated, broken up with a spatula, then stirred in DI water (1.5 L) overnight. The solids were isolated, washed with acetone (200 mL), then dried in a vacuum oven (< 0.01 mm Hg, 60 °C) for 48-hrs. Yield of a light brown solid was 1.95 g (86 %) with a degree of substitution (DS) of 0.87. Anal. Calcd. For C20H31N5O5: C 56.99, H 7.41, N 16.62. Found: C 54.39, H 6.89, N 14.47.

[0160] Synthesis of CELL-TRI-IM-Br (7b)

[0161] In a PTFE-screw-capped pressure vessel was dissolved 6b (1.60 g, 3.80 mmol) in a 10: 1 solution of DMF:DMSO (50 mL total) at 100 °C. Once dissolved (16-20 hr), the stirred solution was cooled to room temperature at ethyl bromide (8.27 g, 75.9 mmol) was added, followed by stirring at 60 °C for 48-hr. The reaction was cooled to room temperature and precipitated onto acetone (1.5 L). The mixture stirred for 1-hr, then the solids were isolated, washed with additional acetone (2 x 250 mL), then dried in a vacuum oven (< 0.01 mm Hg, 60 °C) for 48-hrs, resulting in 2.09 g of an off-white solid (86 %) with a DS of 0.87. Anal. Calcd. For C24H41Br2N5O5: C 45.08, H 6.46, N 10.95. Found: C 43.38, H 6.21, N 9.54.

[0162] Synthesis of CELL-TRI-IM-NTf2(8b)

[0163] In a 250-mL round-bottom flask equipped with a magnetic stir bar was dissolved 7b (1.50 g, 2.35 mmol) in DI water (20 mL) at 60 °C. Upon dissolution, the solution was cooled to room temperature, and a solution of bis(trifluoromethane)sulfonimide lithium salt (2.02 g, 7.04 mmol) in DI water (15 mL) was added slowly by pipette. A solid immediately formed and the resulting solution stirred overnight at room temperature. The solid was isolated, washed with DI water (2 x 25 mL) and dried in a vacuum oven (< 0.01 mm Hg, 60 °C) for 48 hours, resulting in 2.15 g (89%) of a tan solid. The degree of substitution was confirmed to be 0.87 by sulfur content from elemental analysis. The degree of substitution was confirmed to be 0.87 by sulfur content from elemental analysis. Anal. Calcd. For C28H41F12N7O2S4: C 32.34, H 3.97, N 9.43, S 12.33. Found: C 33.94, H 4.11, N 8.10, S 10.77.

[0164] Synthesis of CELL-TRI-IM-ET-NTf2

[0165]

[0166] CELL-TRI-IM-ET-NTf2was prepared according to Schemes 1 and 3-4.

[0167] Synthesis of CELL-TRI-IM-BU-NTf2

[0168] CELL-TRI-IM-BU-NTf2was prepared according to Schemes 1 and 3-4.

[0169] Synthesis of CELL-TRI-C5-NTf2 CELL-TRI-C5-NTf2 was prepared according to Scheme 5.

[0170] Synthesis of CELL-TRI-C5-Br CELL-TRI-C5-Br was prepared according to Scheme 5.

[0171] Synthesis of CELL-TRI-EST-NTf2

[0172] CELL-TRI-EST-NTf2was prepared according to Scheme 5.

[0173] Synthesis of CELL-TRI-OC12-NTf2

[0174] CELL-TRI-OC12-NTf2was prepared according to Scheme 5. Synthesis of CELL-TRI-TEGME-NTf2

[0175] CELL-TRI-TEGME-NTf2was prepared according to Scheme 5.

[0176] Synthesis of CELL-TRI-BNZ-NTf2

[0177] CELL-TRI-BNZ-NTf2was prepared according to Scheme 5.

[0178] Synthesis of CELL-TRI-CYH-NTf2

[0179] CELL-TRI-CYH-NTf2was prepared according to Scheme 5.

[0180] Example 2: Characterization of exemplary dual ionic liquid-functionalized carbohydrate compositions Substituted cellulosic materials were characterized by NMR and IR spectroscopy, as well as elemental analysis.1H NMR spectroscopic data clearly showed the appearance of the aromatic 1,2,3 -triazole and imidazole signals in the 7-8.5 ppm range, indicative of successful ‘click’ cyclization of the alkynyl-substituted imidazoles with CELL-N3. Analysis by IR spectroscopy also showed a disappearance or a significant reduction of the azide stretching vibration at 2110 cm-1and the appearance of a new C=C stretching frequency at -1550 cm-1(FIG. 2 shows the IR spectra for the CELL-C8 series). Elemental analysis indicated that the DS of these materials was on the range of 0.87-0.92 (based upon nitrogen content).

[0181] Quaternization of CELL-CX-tri-im with ethyl bromide resulted in a shift of the aromatic proton signals downfield to 8-9.5 ppm, indicative of the triazolium and imidazolium “ionic liquid” rings. Exchange to the NTf2anion revealed a quartet in the13CNMR spectra indicative of the -CF3group (-120 ppm), and new signals at 1344, 1130, and 602 cm-1(SO2), 738 and 650 cm-1(S-N-S), and 790 cm-1(C-S) in the IR spectra, all of which are characteristic of the NTf2anion. Elemental analysis indicated that DS after anion exchange was 0.87-0.90 across all derivatives as determined from sulfur content.

[0182] Thermal analysis of the exemplary dual-IL functionalized cellulosic material was accomplished using DSC and TGA (Table 1). For reference, data for MCC and mono-IL functionalized cellulose are provided herein. While CELL-C12-tri-im did not exhibit any thermal DSC transitions, subtle Tgvalues were found for the C4 and C8 analogs, and indicated that the slightly longer C8 chain led to a small plasticization effect. Quaternization of the rings resulted in Tgvalues for all three materials and a general decrease in Tgfrom the non-quaternized derivatives.

[0183] Table 1. Thermal properties of exemplary dual-IL functionalized cellulosic materials

[0184] CELL-C4-Br was found to exhibit a 7g value of 69.3 °C and a lengthening of the alkyl tether to C8 lowered the Tgto 37.1 °C; however, further lengthening to C12 resulted in an increase in Tgto 67.3 °C. While the initial decrease in Tgcould be due to plasticization, without wishing to be limited by any theory, the upturn in Tgfrom C8 to C12 may be attributed to an increase in ionic and van der Waals interactions as these longer side chains may intercalate between different cellulose backbones. The trend in Tgacross different alkyl tethers remained the same upon anion exchange; however, an overall decrease in values was observed due to the plasticization ability of the larger, bulkier, hydrophobic anion.

[0185] This relationship between counteranion and Tgmirrors the results observed with mono-IL substituted cellulosic materials; however, the dual-IL functionalized cellulosic materials exhibited lower Tgvalues as the longer chains, coupled with the imidazolium group at the end of the tether, acts to plasticize the system, further breaking up any hydrogen bonding between cellulose backbones.

[0186] Cyclization of CELL-N3 led to a noticeable decrease in thermal stability (Td5%) when compared to the starting microcrystalline cellulose. Additional quaternization of the rings led to another decrease in Td5% value. By quaternizing the ring, a natural retro-SN2 (reverse Menshutkin) decomposition pathway is introduced. This coupled with a more Lewis basic anion such as bromide, resulted in stability only up to ~180 °C. Anion exchange to the less-Lewis basic NTf2anion improved the thermal stability approximately 40-50 °C. Thermal stability of the dual- IL systems were found to be very similar to the mono-IL functionalized analog.

[0187] To evaluate mechanical and conductive properties, films with a thickness of 500 pm and a diameter of 25 pm of each of the respective CELL-CX-NTf2materials were prepared by solvent casting from DMF into a PTFE mold of the appropriate size, resulting in a series of clear, flexible films with light to moderate brown color. These films were first evaluated for their mechanical properties using DMA (dynamic mechanical analysis). Stress-strain analysis of the films (FIG. 3) indicated that CELL-C4-NTf2 exhibited the highest stress at break (2.69 + 0.19 MPa) but the lowest elongation (133 + 14%). Increasing the alkyl chain length led to an increase in flexibility and elongation (up to 252%) with only a small decrease in stress at break. Each film was tested in triplicate with data for each sample provided.

[0188] X-ray scattering data was also acquired for three exemplary dual-IL cellulosic materials, an overlay of which is provided in FIG. 4. WAXS / SAXS combined data analysis indicated that all three materials exhibit amorphous behavior as opposed to microcrystalline cellulose. There are three distinct scattering peaks (q ) present for all three materials. Correlation lengths were calculated from the scattering vector positions using the following equation: dx= 2πlqx(Eq. 1) wherein x refers to the specific type of correlation ( / , II, or III), and the values are presented in Table 2. The high scattering vector, labeled as qI[ (~10-11 nm-1), is assigned to the amorphous halo and occurs due to various interactions between cation / anion pairs and the backbone which are separate from the neutral polymer. As all three cellulosic materials employ the same anion, very little change is observed between these signals and thus the correlation distances are nearly identical. This distance is similar to that which was observed for mono-IL functionalized cellulosic materials. The middle scattering vector, qII, was attributed to the anion-anion distances with a calculated correlation distance of 0.71-0.76 nm. The lowest scattering vector, assigned qIII (~2.5-3.5 nm-1) is assigned to the separation between aggregates. The peak increases dramatically in intensity as the tether spacer changes from C4 to C12 since the increased spacing and hydrophobicity of the backbones leads to stronger, more isolated aggregates.

[0189] Table 2. Scattering vectors (qx) and calculated correlation lengths (dx) for each observable peak from WAXS / SAXS combined X-ray scattering profiles for certain exemplary CELL-Cx-NTf2cellulosic materials Conductivity of ion-containing polymers depends upon both the diffusion and concentration of ion species. A combination of other factors, many of which are difficult to separate, also contribute to conductivity, including Tg, polymer morphology and structure, and ion aggregation. The ionic conductivity values provided herein were determined using the dielectric accessory of a rheometer under an atmosphere of dry nitrogen. Each sample was allowed to equilibrate at the desired temperature (130 to -10 °C in 10 °C steps) for 45-minutes prior to obtaining any data. As shown in FIG. 5A (top), ionic conductivity was found to be on the order of 10-7to 10-6S / cm at 30 °C. For reference, conductivity data for certain mono-1,2,3- triazolium IL substituted cellulose [NTf2] material is also provided.

[0190] Comparing the curves in FIG. 5A (top) of the three dual-IL cellulosic materials, the ionic conductivities of the CELL-C8-NTf2and CELL-C12-NTf2analogs were found to be parallel curves with the C8 derivative exhibiting a slightly higher conductivity, presumably due to its lower Zg-value. The conductivity curve for CELL-C4-NTf2exhibited slightly different behavior. At lower temperatures, the C4 derivative was found to be the lowest conductor, but then, as temperature increased, the conductivity crossed over the C8 and C12 derivatives, resulting in the highest conductivity at elevated temperatures. Ionic conductivity was further plotted as a function of normalized Tg(FIG. 5B). Note that the C8 and C12 derivative curves effectively coalesce, emphasizing that conductivity is heavily dependent on Tg. However, CELL-C4-NTf2exhibits the highest Tg-normalized conductivity and does not coalesce well with the other data sets, especially at higher temperatures. As the three materials have a negligible difference in ion concentration and the polymer backbone (cellulose) and degree of substitutions are essentially the same, ion aggregation is believed to be a major attribute in affecting ionic conductivity. We hypothesis that discrete aggregate clusters are being formed in both CELL-C12-NTf2and CELL-C8-NTf2, resulting in electrostatic / Coulombic interactions that are more difficult to overcome, even at higher temperatures. The longer, hydrophobic alkyl chain lengths force the ions into clusters which are not interconnected, leading to poor ion hopping throughout the matrix. As CELL-C4-NTf2utilizes the shortest tether, the counteranions are either not present in isolated clusters or the clusters must be interconnected (this distinction cannot be made with the present data), allowing for a greater increase in conductivity with temperature.

[0191] In comparison with the previously reported mono-IL cellulosic material, the inclusion of the second (imidazolium) IL group results in two noticeable changes in the conductivity data. First, the CELL-Cx-NTf2materials exhibit conductivities which are approximately an order of magnitude higher than the mono-IL analog across most of the same temperature range. Secondly, the CELL-Cx-NTf2materials exhibit a non-linear response to temperature unlike the linear (Arrhenius) behavior shown by the mono-IL analog. As all of the CELL-Cx-NTf2materials exhibited Tgvalues below 0 °C, all of the conductivity data presented here were completed above the Tg, meaning that the dual IL-containing polymers rely on not only the “hopping” of free ions along the backbone of the polymer but also on other segmental motion and relaxation events of the polymer itself. This leads to a response which follows Vogel-Fulcher-Tamman (VFT) behavior as defined by the following equation: σ( T) = σ∞x exp(-D TolT-To) (Eq. 2) wherein σ∞is the infinite conductivity limit, D is the strength parameter, Tois the Vogel temperature (the temperature in which ion mobility goes to zero and polymer relaxation time is infinite) and T is the experimental temperature. VFT-fits for each of the CELL-Cx-NTf2materials are provided as solid curves in FIG. 5A (top) with fitting parameters provided in Table 3. High temperature limiting conductivity values (o"co) increase with decreasing alkyl tether length with CELL-C4-NTf2exhibiting the highest value. As described elsewhere herein, this system appears to have the least amount of ionic aggregation, meaning that, as the temperature increases, there must exist a higher degree of ion mobility. Other VFT fitting parameters, Tg- T0and D (strength parameter) values, were found to be similar to other poly(ionic liquid)s, ionenes, and IL-containing networks reported in the literature with no discernable trend amongst the three derivatives.

[0192] Table 3. VFT fitting parameters for certain exemplary CELL-Cx-NTf2cellulosic materials

[0193] Example 3: Shape recovery of certain exemplary dual ionic liquid-functionalized carbohydrate compositions in response to mechanical deformation

[0194] In certain embodiments, films were prepared using exemplary dual ionic liquid- functionalized cellulose materials. In certain embodiments, the films can be prepared in any of a number of shapes, including but not limited to helical shapes (FIG. 6A). In certain embodiments, the original shape of the fdm (e.g., helix) can be at least partially deformed by application of mechanical force. In certain embodiments, the films described herein recover the original shape (e.g., helix) after mechanical deformation after a period of about 1 week at room temperature (FIGs. 6B-6D).

[0195] In certain embodiments, a flat, rectangular film comprising the ionic liquid-functionalized cellulosic material can be molded and held in a particular shape (e.g., helical shape). For example, a helical shape can be obtained according to the procedures described herein. A rectangular cellulosic material film of the present disclosure is wrapped around a glass or Teflon rod, the end(s) are clamped (e.g., using binder clips), and the film heated gently for about 1-2 minutes (e.g., about 40-60 °C). Next, the sample is placed in a freezer (e.g., about -20 °C) for about 5 minutes. The binder clips are then removed, and the materials is removed from the rod, resulting in a fixed helical shape (FIG. 6B). Upon heating the helix gentle for about 1-2 minutes (e.g., about 40-60 °C), the material will return to its original flag, rectangular shape.

[0196] To conduct shape memory experiments, dynamic mechanical analysis (DMA) under controlled-strain mode was utilized. In the first step, a rectangular piece of film was heated from room temperature to 40 °C. The strain was increased at a speed of 100% / min in order to maintain 10% of the elongated length. During the third step, the temperature was reduced to -40 °C under constant strain, and maintained for 10 min. This was followed by releasing the external stress. Shape recovery of the film was accomplished by heating to 40 °C for 30 min. This process is repeated several cycles (FIG. 6C).

[0197] Shape fixing behavior is quantified via the shape fixing ratio RF, which is the ratio of the strain after unloading and the strain at the shape fixing temperature (-40 °C) as shown in FIG. 6D. Shape recovery is achieved by heating the material to a temperature higher than the transition temperature without stress. Shape recovery is quantified via the shape recovery ratio (RR), which is defined as the ratio between the strain recovered and the fixed strain under stress at the deformation temperature (40 °C).

[0198] RF= (ε / εload) x 100 (Eq. 3)

[0199] RR= (ε - εrec / ε - εi) X 100 (Eq. 4) where εload, ε, εrec, and εirepresents the maximum strain under load, fixed strain after cooling and unloading, strain after recovery, and initial strain at 40 °C. Enumerated Embodiments

[0200] The following exemplary embodiments are provided, the numbering of which is not to be construed as designating levels of importance:

[0201] Embodiment 1 provides a compound of formula (I), or a salt, solvate, stereoisomer, or isotopologue thereof wherein: each occurrence of R1aand R1bis independently selected from the group consisting of

[0202] OH, NH2, NS, , and wherein less than about 50% of the R1aand R1bsubstituents are OH, NH2, or N3; each occurrence of L1, L2, and L3is independently selected from the group consisting of optionally substituted C1-C12alkylenyl and optionally substituted C1-C12heteroalkylenyl; each occurrence of Y1and Y2is independently selected from the group consisting of O and NR2e;

[0203] R2a, R2b, R2C, R2d, and R2eare each independently selected from the group consisting of H, optionally substituted C1-C6alkyl, and C(=O)(optionally substituted C1-C6alkyl); each occurrence of A1is independently selected from the group consisting of

[0204] each occurrence of R3aand R3bis independently selected from the group consisting of optionally substituted C1-C12alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of R4a, R4b, and R4cis independently selected from the group consisting of H, halogen, CN, NO2, ORA, N(RA)(RB), SRA, C(=O)ORA, C(=O)RA, C(=O)N(RA)(RB), S(=O)2RA, S(=O)2ORA, S(=O)2N(RA)(RB), S(=O)RA, S(=O)N(RA)(RB), P(=O)(ORA)(ORB), optionally substituted C1-C6alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of X1is independently a counter anion;

[0205] A2is selected from the group consisting of each occurrence of R5a, R5b, and R5cis independently selected from the group consisting of optionally substituted C1-C12alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted Cs-Cio aryl, and optionally substituted C2-C10heteroaryl; each occurrence of R6a, R6band R6cis independently selected from the group consisting of H, halogen, CN, NO2, ORC, N(RC)(RD), SRC, C(=O)ORc, C(=O)RC, C(=O)N(Rc)(RD), S(=O)2RC, S(=O)2ORC, S(=O)2N(RC)(RD), S(=O)RC, S(=O)N(RC)(RD), P(=O)(ORC)(ORD), optionally substituted C1-C6alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of T is independently selected from the group consisting of optionally substituted C1-C12alkyl and optionally substituted C1-C12alkoxy each occurrence of X2is independently a counter anion; each occurrence of RA, RB, Rc, and RDis independently selected from the group consisting of H, optionally substituted C1-C6alkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; m is an integer ranging from 100 to 10,000; each occurrence of n is an integer ranging from 1 to 200.

[0206] Embodiment 2 provides the compound of Embodiment 1, wherein the compound of formula (I) is a compound of formula (la):

[0207] Embodiment 3 provides the compound of Embodiment 1 or 2, wherein each occurrence of L1and L2is independently -CH2- or -CH2OCH2CH2-.

[0208] Embodiment 4 provides the compound of any one of Embodiments 1-3, wherein each occurrence of R2a, R2b, R2c, R2d, and R2eis independently H.

[0209] Embodiment 5 provides the compound of any one of Embodiments 1-4, wherein each occurrence of Y1and Y2is independently selected from the group consisting of -O- and -NH-. Embodiment 6 provides the compound of any one of Embodiments 1 -5, wherein each occurrence of R3aand R3bis independently C1-C6alkyl, optionally wherein each occurrence of R3aand R3bis independently ethyl or butyl.

[0210] Embodiment 7 provides the compound of any one of Embodiments 1-6, wherein each occurrence of R4a, R4b, and R4cis independently selected from the group consisting of H, -

[0211] (CH2)1-5CH3, -CH(CH3)2, -CH2CH(CH3)2, -(CH2CH20)I-6(CH2)O-5CH3, , and

[0212] Embodiment 8 provides the compound of any one of Embodiments 1-7, wherein each occurrence of X1is independently selected from the group consisting of N(S(=O)2CF3)2(NTf2), OS(=O)2CF3(OTf), OC(=O)CH3(OAC), OC(=O)CF3, N(CN)2, PF6, BF4, OH, HCO3, and Br.

[0213] Embodiment 9 provides the compound of any one of Embodiments 1-8, wherein each occurrence of A is independently selected from the group consisting of and

[0214] Embodiment 10 provides the compound of any one of Embodiments 1-9, wherein each occurrence of R5a, R5b, and R3cis independently C1-C6alkyl, optionally wherein each occurrence of R5aand R5bis independently ethyl.

[0215] Embodiment 11 provides the compound of any one of Embodiments 1-10, wherein each occurrence of R6a, R6b, and R6cis independently selected from the group consisting of H, -

[0216] (CH2)1-5CH3, -CH(CH3)2, -CH2CH(CH3)2, -(CH2CH20)I-6(CH2)O-5CH3, and

[0217] Embodiment 12 provides the compound of any one of Embodiments 1-11, wherein each occurrence of X2is independently selected from the group consisting of N(S(=O)2CF3)2(NTf2), OS(=O)2CF3(OTf), OC(=O)CH3(OAC), OC(=O)CF3, N(CN)2, PF6, BF4, OH, HCO3, and Br. Embodiment 13 provides the compound of any one of Embodiments 1-12, wherein each occurrence of A2is independently selected from the group consisting of and

[0218] Embodiment 14 provides the compound of any one of Embodiments 1-13, wherein each occurrence of L3is independently selected from the group consisting of -(CH2)-, -CH2O(CH2)2-, -CH2O(CH2)4-, -CH2O(CH2)8-, and -(CH2)4-.

[0219] Embodiment 15 provides the compound of any one of Embodiments 1-14, wherein n is 1.

[0220] Embodiment 16 provides the compound of any one of Embodiments 1-15, wherein each occurrence of R1aand R1bis independently selected from the group consisting of

[0221] Embodiment 17 provides the compound of any one of Embodiments 1-9 and 14, wherein each occurrence of T is independently selected from the group consisting of

[0222] Embodiment 18 provides the compound of any one of Embodiments 1-9, 14, and 17, wherein each occurrence of R1aand R1bis independently selected from the group consisting of

[0223]

[0224] Embodiment 19 provides a film comprising the compound of any one of Embodiments 1-

[0225] 18.

[0226] Embodiment 20 provides the film of Embodiment 19, wherein the film is at least partially resistant to mechanical deformation.

[0227] Embodiment 21 provides the film of Embodiment 19 or 20, wherein the film at least partially recovers to an original shape after mechanical deformation.

[0228] Embodiment 22 provides a powder comprising the compound of any one of Embodiments 1-18.

[0229] Embodiment 23 provides a fiber comprising the compound of any one of Embodiments 1-18.

[0230] Embodiment 24 provides a method of sequestering carbon dioxide (CO2) and / or separating CO2from a mixture comprising CO2and at least one additional gas, the method comprising contacting the compound of any one of Embodiments 1-18, the film of any one of Embodiments 19-21, the powder of Embodiment 22, or the fiber of Embodiment 23 with the mixture.

[0231] Embodiment 25 provides the method of Embodiment 24, wherein the additional gas comprises at least one selected from the group consisting of nitrogen (N2) and oxygen (O2).

[0232] Embodiment 26 provides the method of Embodiment 24 or 25, wherein the mixture comprises air.

[0233] The terms and expressions employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the embodiments of the present application. Thus, it should be understood that although the present application describes specific embodiments and optional features, modification and variation of the compositions, methods, and concepts herein disclosed may be resorted to by those of ordinary skill in the art, and that such modifications and variations are considered to be within the scope of embodiments of the present application.

Claims

CLAIMSWhat is claimed is:

1. A compound of formula (I), or a salt, solvate, stereoisomer, or isotopologue thereof:wherein: each occurrence of R1aand R1bis independently selected from the group consisting ofOH, NH2, N3,, andwherein less than about 50% of the R1aand R1bsubstituents are OH, NH2, or N3; each occurrence of L1, L2, and L3is independently selected from the group consisting of optionally substituted C1-C12alkylenyl and optionally substituted C1-C12heteroalkylenyl; each occurrence of Y1and Y2is independently selected from the group consisting of O and NR2e;R2a, R2b, R2C, R2d, and R2eare each independently selected from the group consisting of H, optionally substituted C1-C6alkyl, and C(=O)(optionally substituted C1-C6alkyl); each occurrence of A1is independently selected from the group consisting ofeach occurrence of R3aand R3bis independently selected from the group consisting of optionally substituted C1-C12alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of R4a, R4b, and R4cis independently selected from the group consisting of H, halogen, CN, NO2, ORA, N(RA)(RB), SRA, C(=O)ORA, C(=O)RA, C(=O)N(RA)(RB), S(=O)2RA, S(=O)2ORA, S(=O)2N(RA)(RB), S(=O)RA, S(=O)N(RA)(RB), P(=O)(ORA)(ORB), optionally substituted C1-C6alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of X1is independently a counter anion;A2is selected from the group consisting ofeach occurrence of R5a, R5b, and R5cis independently selected from the group consisting of optionally substituted C1-C12alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of R6a, R6band R6cis independently selected from the group consisting of H, halogen, CN, NO2, ORC, N(RC)(RD), SRC, C(=O)ORc, C(=O)Rc, C(=O)N(Rc)(RD), S(=O)2RC, S(=O)2ORC, S(=O)2N(RC)(RD), S(=O)RC, S(=O)N(RC)(RD), P(=O)(ORC)(ORD),optionally substituted C1-C6alkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; each occurrence of T is independently selected from the group consisting of optionally substituted C1-C12alkyl and optionally substituted C1-C12alkoxy; each occurrence of X2is independently a counter anion; each occurrence of RA, RB, Rc, and RDis independently selected from the group consisting of H, optionally substituted C1-C6alkyl, optionally substituted C1-C6heteroalkyl, optionally substituted C3-C8cycloalkyl, optionally substituted C2-C8heterocycloalkyl, optionally substituted C6-C10aryl, and optionally substituted C2-C10heteroaryl; m is an integer ranging from 100 to 10,000; each occurrence of n is independently an integer ranging from 1 to 200.

2. The compound of claim 1, wherein the compound of formula (I) is a compound of formula (la):

3. The compound of claim 1 or 2, wherein each occurrence of L1and L2is independently - CH2- or -CH2OCH2CH2-.

4. The compound of any one of claims 1-3, wherein each occurrence of R2a, R2b, R2c, R2d, and R2eis independently H.

5. The compound of any one of claims 1-4, wherein each occurrence of Y1and Y2is independently selected from the group consisting of -O- and -NH-.

6. The compound of any one of claims 1-5, wherein each occurrence of R3aand R3bis independently C1-C6alkyl, optionally wherein each occurrence of R3aand R3bis independently ethyl or butyl.

7. The compound of any one of claims 1-6, wherein each occurrence of R4a, R4b, and R4eis independently selected from the group consisting of H, -(CH2)I-5CH3, -CH(CH3)2, -CH2CH(CH3)2, -(CH2CH20)I-6(CH2)O-5CH3,8. The compound of any one of claims 1-7, wherein each occurrence of X1is independently selected from the group consisting of N(S(=O)2CF3)2(NTf2), OS(=O)2CF3(OTf), 0C(=0)CH3(OAc), OC(=O)CF3, N(CN)2, PF6, BF4, OH, HCO3, and Br.

9. The compound of any one of claims 1-8, wherein each occurrence of A1is independently selected from the group consisting of10. The compound of any one of claims 1-9, wherein each occurrence of R5a, R5b, and R3Cis independently C1-C6alkyl, optionally wherein each occurrence of R5aand R5bis independently ethyl.

11. The compound of any one of claims 1-10, wherein each occurrence of R6a, R6b, and R6cis independently selected from the group consisting of H, -(CH2)I-SCH3, -CH(CH.3)2, -CH2CH(CH3)2, -(CH2CH20)I-6(CH2)O-5CH3,12. The compound of any one of claims 1-11, wherein each occurrence of X2is independently selected from the group consisting of N(S(=O)2CF3)2(NTf2), OS(=O)2CF3(OTf), OC(=O)CH3(OAC), OC(=O)CF3, N(CN)2, PF6, BF4, OH, HCO3, and Br.

13. The compound of any one of claims 1-12, wherein each occurrence of A2is independently selected from the group consisting of14. The compound of any one of claims 1-13, wherein each occurrence of L3is independently selected from the group consisting of -CH2O(CH2)2-, -CH2O(CH2)4-, - CH2O(CH2)8-, and -(CH2)4-.

15. The compound of any one of claims 1-14, wherein n is 1.

16. The compound of any one of claims 1-15, wherein each occurrence of R1aand R1bis independently selected from the group consisting of17. The compound of any one of claims 1-9 and 14, wherein each occurrence of T is independently selected from the group consisting of18. The compound of any one of claims 1-9, 14, and 17, wherein each occurrence of R1aand R1bis independently selected from the group consisting of19. A film comprising the compound of any one of claims 1-18.

20. The film of claim 19, wherein the film is at least partially resistant to mechanical deformation.

21. The film of claim 19 or 20, wherein the film at least partially recovers to an original shape after mechanical deformation.

22. A powder comprising the compound of any one of claims 1-18.

23. A fiber comprising the compound of any one of claims 1-18.

24. A method of sequestering carbon dioxide (CO2) and / or separating CO2from a mixture comprising CO2and at least one additional gas, the method comprising contacting the compound of any one of claims 1-18, the film of any one of claims 19-21, the powder of claim 22, or the fiber of claim 23 with the mixture.

25. The method of claim 24, wherein the additional gas comprises at least one selected from the group consisting of nitrogen (N2) and oxygen (O2).

26. The method of claim 24 or 25, wherein the mixture comprises air.

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